Synergistic pesticidal compositions and related methods

ABSTRACT

A pesticidal composition comprises a synergistically effective amount of a ryanodine receptor modulator compound and a pesticide selected from N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I), N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (II), or any agriculturally acceptable salt thereof. A method of controlling pests comprises applying the pesticidal composition near a population of pests. A method of protecting a plant from infestation and attack by insects comprises contacting the plant with the synergistic pesticidal composition.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.14/516,855 filed on Oct. 17, 2014, which claims the benefit of U.S.Provisional Patent Application Ser. No. 61/894,016, filed Oct. 22, 2013,the disclosures of each are hereby incorporated herein in their entiretyby this reference.

TECHNICAL FIELD

This disclosure relates to the field of compounds having pesticidalutility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca,processes to produce such compounds and intermediates used in suchprocesses. These compounds may be used, for example, as nematicides,acaricides, miticides, and/or molluscicides.

BACKGROUND

Controlling pest populations is essential to human health, modernagriculture, food storage, and hygiene. There are more than ten thousandspecies of pests that cause losses in agriculture and the worldwideagricultural losses amount to billions of U.S. dollars each year.Accordingly, there exists a continuous need for new pesticides and formethods of producing and using such pesticides.

The Insecticide Resistance Action Committee (IRAC) has classifiedinsecticides into categories based on the best available evidence of themode of action of such insecticides. Insecticides in the IRAC Mode ofAction Group 28 are ryanodine receptor modulators, which target thenerve and muscles of the affected insects. The insecticides in thisclass are believed to activate muscle ryanodine receptors, leading tocontraction and paralysis of the affected insects. Examples ofinsecticides in this class are diamides, such as chlorantraniliprole,cyantraniliprole, cyclaniliprole, and flubendiamide.

Chlorantraniliprole(3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide)is an anthranilic diamine insecticide. It has been reported as aninsecticide to control a broad range of pests belonging to the OrderLepidoptera and some Coleoptera, Diptera and Isoptera species.

Cyantraniliprole(3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide)is an anthranilic diamine insecticide. It is believed to have aninsecticidal activity on a broad range of Lepidoptera, Coleoptera,Diptera, and Isoptera insects.

Although the rotational application of pesticides having different modesof action may be adopted for good pest management practice, thisapproach does not necessarily give satisfactory pest control.Furthermore, even though combinations of pesticides have been studied, ahigh synergistic action has not always been found.

DETAILED DESCRIPTION

As used herein, the term “synergistic effect” or grammatical variationsthereof means and includes a cooperative action encountered in acombination of two or more active compounds in which the combinedactivity of the two or more active compounds exceeds the sum of theactivity of each active compound alone.

The term “synergistically effective amount,” as used herein, means andincludes an amount of two or more active compounds that provide asynergistic effect defined above.

The term “pesticidally effective amount,” as used herein, means andincludes an amount of active pesticide that causes an adverse effect tothe at least one pest, wherein the adverse effect may include deviationsfrom natural development, killing, regulation, or the like.

As used herein, the term “control” or grammatical variations thereofmeans and includes regulating the number of living pests or regulatingthe number of viable eggs of the pests or both.

The term “ryanodine receptor modulator compound,” as used herein, meansand includes any insecticides that are classified by the InsecticideResistance Action Committee (IRAC), based on the best available evidenceof the mode of action, to be within the IRAC Mode of Action Group 28.

In one particular embodiment, a pesticidal composition comprises asynergistically effective amount of a ryanodine receptor modulatorcompound in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

It is appreciated that a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof may be oxidized tothe corresponding sulfone in the presence of oxygen.

As shown in the examples, the existence of synergistic effect isdetermined using the method described in Colby S. R., “CalculatingSynergistic and Antagonistic Responses of Herbicide Combinations,”Weeds, 1967, 15, 20-22.

Surprisingly, it has been found that the pesticidal composition of thepresent disclosure has superior pest control at lower levels of thecombined concentrations of the ryanodine receptor modulator compound andthe pesticide (I), (II), or any agriculturally acceptable salt thereofemployed than that which may be achieved when the ryanodine receptormodulator compound and the pesticide (I), (II), or any agriculturallyacceptable salt thereof are applied alone. In other words, thesynergistic pesticidal composition is not a mere admixture of two activecompounds resulting in the aggregation of the properties of the activecompounds employed in the composition.

In some embodiments, the pesticidal compositions may comprise asynergistically effective amount of a pesticide selected from (I), (II),or any agriculturally acceptable salt thereof in combination withcyantraniliprole. In other embodiments, the pesticidal compositions maycomprise a synergistically effective amount of a pesticide selected from(I), (II), or any agriculturally acceptable salt thereof in combinationwith chlorantraniliprole.

TABLE 1A Range of the Weight Ratio of No. Pesticide I or II to RyanodineReceptor Modulator Compound 1 20:1 to 1:20 2 15:1 to 1:15 3 10:1 to 1:104 5:1 to 1:5 5 4:1 to 1:4 6 3:1 to 1:3 7 2:1 to 1:2 8 1:1

Table 1A shows weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the ryanodine receptormodulator in the synergistic pesticidal compositions. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 20:1 and about 1:20. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 15:1 and about 1:15. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 10:1 and about 1:10. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 5:1 and about 1:5. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 4:1 and about 1:4. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 3:1 and about 1:3. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be between about 2:1 and about 1:2. In someembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be about 1:1. Additionally, the weight ratiolimits of the pesticide to ryanodine receptor modulator compound in theaforementioned embodiments may be interchangeable. By way ofnon-limiting example, the weight ratio of the pesticide to the ryanodinereceptor modulator compound may be between about 1:3 and about 20:1.

Weight ratios of the pesticide (I), (II), or any agriculturallyacceptable salt thereof to the ryanodine receptor modulator envisionedto be synergistic pesticidal compositions may be depicted as X:Y;wherein X is the parts by weight of the pesticide (I), (II), or anyagriculturally acceptable salt thereof, and Y is the parts by weight ofthe ryanodine receptor modulator. The numerical range of the parts byweight for X is 0<X≦20 and the parts by weight for Y is 0<Y≦20 as showngraphically in TABLE 1B. By way of non-limiting example, the weightratio of the pesticide to the ryanodine receptor modulator compound maybe about 20:1.

TABLE 1B Ryanodine 20 X, Y X, Y Receptor 15 X, Y X, Y X, Y Modulator 10X, Y X, Y (Y) Parts 5 X, Y X, Y X, Y X, Y by weight 4 X, Y X, Y X, Y X,Y 3 X, Y X, Y X, Y X, Y X, Y X, Y 2 X, Y X, Y X, Y X, Y 1 X, Y X, Y X, YX, Y X, Y X, Y X, Y X, Y 1 2 3 4 5 10 15 20 Pesticide (I or II) (X)Parts by weight

Ranges of weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the ryanodine receptormodulator envisioned to be synergistic pesticidal compositions may bedepicted as X₁:Y₁ to X₂:Y₂, wherein X and Y are defined as above. In oneparticular embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁>Y₁ and X₂<Y₂. By way of non-limiting example, the range ofweight ratios of the pesticide to the ryanodine receptor modulatorcompound may be between about 3:1 and about 1:3. In some embodiments,the range of weight ratios may be X₁:Y₁ to X₂:Y₂, wherein X₁>Y₁ andX₂>Y₂. By way of non-limiting example, the range of weight ratios of thepesticide to the ryanodine receptor modulator compound may be betweenabout 15:1 and about 3:1. In further embodiments, the range of weightratios may be X₁:Y₁ to X₂:Y₂, wherein X₁<Y₁ and X₂<Y₂. By way ofnon-limiting example, the range of weight ratios of the pesticide to theryanodine receptor modulator compound may be between about 1:3 and about1:20.

Table 1C shows weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the ryanodine receptormodulator compound in the synergistic pesticidal compositions, accordingto particular embodiments of the present disclosure. In some particularembodiments, the weight ratio of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the ryanodine receptormodulator compound may be no more than about 256:1. In furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 72:1. In furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 32:1. In furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 16:1. In furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 8:1. In furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 6:1. In furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 4:1. In yet furtherembodiments, the weight ratio of the pesticide to the ryanodine receptormodulator compound may be no more than about 2:1.

TABLE 1C Dose Rate of Weight Ratio of Dose Rate Of Ryanodine Pesticide(I or II) to Pesticide (I or II) Receptor Modulator Ryanodine Receptor(weight %) (weight %) Modulator 0.04 0.000156 ≦256:1 0.0025 0.0000347 ≦72:1 0.0025 0.0000781  ≦32:1 0.0025 0.000156  ≦16:1 0.0025 0.0003125 ≦8:1 0.000625 0.0000781  ≦8:1 0.000625 0.000104  ≦6:1 0.000625 0.000156 ≦4:1 0.000625 0.0003125  ≦2:1

The weight ratio of the pesticide (I), (II), or any agriculturallyacceptable salt thereof to the ryanodine receptor modulator compound inthe synergistic pesticidal composition may be varied and different fromthose described in Table 1A, Table 1B, and Table 1C. One skilled in theart recognizes that the synergistic effective amount of the combinationof active compounds may vary accordingly to various prevailingconditions. Non-limiting examples of such prevailing conditions mayinclude the type of pests, the type of crops, the mode of application,the application timing, the weather conditions, the soil conditions, thetopographical character, or the like. It is understood that one skilledin the art may readily determine the synergistic effective amount of theryanodine receptor modulator compound and the pesticide (I), (II), orany agriculturally acceptable salt thereof accordingly to the prevailingconditions.

In some embodiments, the pesticidal compositions may comprise asynergistically effective amount of cyantraniliprole in combination witha pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In other embodiments, the pesticidal compositions may comprise asynergistically effective amount of chlorantraniliprole in combinationwith a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In alternative embodiments, the pesticidal composition may comprise asynergistically effective amount of a ryanodine receptor modulatorcompound in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and aphytologically-acceptable inert carrier (e.g., solid carrier, or liquidcarrier).

In further embodiments, the pesticidal composition may further compriseat least one additive selected from a surfactant, a stabilizer, anemetic agent, a disintegrating agent, an antifoaming agent, a wettingagent, a dispersing agent, a binding agent, dye, filler, or combinationsthereof

In particular embodiments, each of the pesticides (a ryanodine receptormodulator compound, and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof) may be formulatedseparately as a wettable powder, emulsifiable concentrate, aqueous orliquid flowable, suspension concentrate or any one of the conventionalformulations used for pesticides, and then tank-mixed in the field withwater or other liquid for application as a liquid spray mixture. Whendesired, the separately formulated pesticides may also be appliedsequentially.

In some embodiments, the synergistic pesticidal composition may beformulated into a more concentrated primary composition, which is thendiluted with water or other diluent before use. In such embodiments, thesynergistic pesticidal composition may further comprise a surface activeagent.

In one particular embodiment, the method of protecting a plant frominfestation and attack by insects comprises contacting the plant with apesticidal composition comprising a synergistically effective amount ofa ryanodine receptor modulator compound in combination with a pesticideselected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In some embodiments, the pesticidal compositions may be in the form ofsolid. Non-limiting examples of the solid forms may include powder, dustor granular formulations.

In other embodiments, the pesticidal compositions may be in the form ofliquid formulation. Examples of the liquid forms may include, but notlimited to, dispersion, suspension, emulsion or solution in appropriateliquid carrier. In particular embodiments, the synergistic pesticidalcompositions may be in the form of liquid dispersion, wherein thesynergistic pesticidal compositions may be dispersed in water or otheragriculturally suitable liquid carrier.

In certain embodiments, the synergistic pesticidal compositions may bein the form of solution in an appropriate organic solvent. In oneembodiment, the spray oils, which are widely used in agriculturalchemistry, may be used as the organic solvent for the synergisticpesticidal compositions.

In one particular embodiment, the method of controlling pests comprisesapplying a pesticidal composition near a population of pests, whereinthe pesticidal composition comprises a synergistically effective amountof a ryanodine receptor modulator compound in combination with apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

The control of pests may be achieved by applying a pesticidallyeffective amount of the synergistic pesticidal compositions in form ofsprays, topical treatment, gels, seed coatings, microcapsulations,systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols,dusts, or the like.

These disclosed pesticidal compositions may be used, for example, asnematicides, acaricides, miticides, and/or molluscicides.

The pesticidal composition of the present disclosure may be used tocontrol a wide variety of insects. As a non-limiting example, in one ormore embodiments, the pesticidal composition may be used to control oneor more members of at least one of Phylum Arthropoda, Phylum Nematoda,Subphylum Chelicerata, Subphylum Myriapoda, Subphylum Hexapoda, ClassInsecta, Class Arachnida, and Class Symphyla. In at least someembodiments, the method of the present disclosure may be used to controlone or more members of at least one of Class Insecta and ClassArachnida.

As a non-limiting example, in one or more embodiments, the method of thepresent disclosure may be used to control one or more members of atleast one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata,Subphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida,and Class Symphyla. In at least some embodiments, the method of thepresent disclosure may be used to control one or more members of atleast one of Class Insecta and Class Arachnida.

In additional embodiments, the method of the present disclosure may beused to control members of the Order Coleoptera (beetles) including, butnot limited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus(common bean weevil), Agrilus planipennis (emerald ash borer), Agriotesspp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle),Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidiusspp., Apion spp. (weevils), Apogonia spp. (grubs), Ataenius spretulus(Black Turfgrass Ataenius), Atomana lineans (pygmy mangold beetle),Aulacophore spp., Bothynoderes punctiventris (beet root weevil), Bruchusspp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp.,Callosobruchus maculatus (southern cow pea weevil), Carpophilushemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp.,Cerotoma spp. (chrysomelids), Cerotoma trifurcata (bean leaf beetle),Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpodweevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp.(chrysomelids), Colaspis spp. (soil beetles), Conoderus scalaris,Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinusnitidis (Green June beetle), Crioceris asparagi (asparagus beetle),Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pusillus(flat grain beetle), Cryptolestes turcicus (Turkish grain beetle),Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp.(grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporausmarginatus (mango leaf-cutting weevil), Dermestes lardarius (larderbeetle), Dermestes maculates (hide beetle), Diabrotica spp.(chrysomelids), Epilachna varivestis (Mexican bean beetle), Faustinuscubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hyperapostica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricome (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana (chrysomelids), Phynchites spp.,Popillia japonica (Japanese beetle), Prostephanus truncates (largergrain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogusspp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp.(wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leafweevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granaryweevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstorebeetle), Tribolium spp. (flour beetles), Tribolium castaneum (red flourbeetle), Tribolium confusum (confused flour beetle), Trogodermavariabile (warehouse beetle), and Zabrus tenebioides.

In other embodiments, the method of the present disclosure may also beused to control members of the Order Dermaptera (earwigs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Dictyoptera (cockroaches)including, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Diptera (true flies) including, but isnot limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfablotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp.(fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp.(mosquitoes), Bactrocera spp. (fruit flies), Bactrocera cucurbitae(melon fly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp.(fruit flies), Ceratitis capitata (Mediterranean fruit fly), Chrysopsspp. (deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gallmidges), Culex spp. (mosquitoes), Dasineura spp. (gall midges),Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura(seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filthflies), Fannia canicularis (little house fly), Fannia scalaris (latrinefly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae,Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypodermalineatum (common cattle grub), Liriomyza spp. (leafminer flies),Liriomyza brassica (serpentine leafminer), Liriomyza sativae (vegetableleafminer), Melophagus ovinus (sheep ked), Musca spp. (muscid flies),Musca autumnalis (face fly), Musca domestica (house fly), Oestrus ovis(sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beetleafminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletiscerasi (cherry fruit fly), Rhagoletis pomonella (apple maggot),Sitodiplosis mosellana (orange wheat blossom midge), Stomoxys calcitrans(stable fly), Tabanus spp. (horse flies), and Tipula spp. (crane flies).

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hemiptera Sub-order Heteroptera (truebugs) including, but is not limited to, Acrosternum hilare (green stinkbug), Blissus leucopterus (chinch bug), Bragada hilaris, Calocorisnorvegicus (potato mind), Cimex hemipterus (tropical bed bug), Cimexlectularius (bed bug), Dagbertus fasciatus, Dichelops furcatus,Dysdercus suturellus (cotton stainer), Edessa meditabunda, Eurygastermaura (cereal bug), Euschistus heros, Euschistus servus (brown stinkbug), Helopeltis antonii, Helopeltis theivora (tea blight plantbug),Lagynotomus spp. (stink bugs), Leptocorisa oratorius, Leptocorisavaricomis, Lygus spp. (plant bugs), Lygus hesperus (western tarnishedplant bug), Lygus lineolaris (tarnished plant bug), Maconellicoccushirsutus, Neurocolpus longirostris, Nezara viridula (southern greenstink bug), Phytocoris spp. (plant bugs), Phytocoris californicus,Phytocoris relativus, Piezodorus guildinii (redbanded stink bug),Poecilocapsus lineatus (fourlined plant bug), Psallus vaccinicola,Pseudacysta perseae, Scaptocoris castanea, and Triatoma spp.(bloodsucking conenose bugs/kissing bugs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Hemiptera, Sub-ordersAuchenorrhyncha (Free-living Hemipterans) and Sternorrhyncha(Plant-parasitic Hemipterans) (aphids, scales, whiteflies, leaflhoppers)including, but is not limited to, Acrythosiphon pisum (pea aphid),Adelges spp. (adelgids), Aleurodes proletella (cabbage whitefly),Aleurodicus disperses, Aleurothrixus floccosus (woolly whitefly),Aluacaspis spp., Amrasca bigutella bigutella, Aphrophora spp.(leafhoppers), Aonidiella aurantii (California red scale), Aphis spp.(aphids), Aphis gossypii (cotton aphid), Aphis pomi (apple aphid),Aulacorthum solani (foxglove aphid), Bemisia spp. (whiteflies), Bemisiaargentifolii, Bemisia tabaci (sweetpotato whitefly), Brachycolus noxius(Russian aphid), Brachycorynella asparagi (asparagus aphid), Brevenniarehi, Brevicoryne brassicae (cabbage aphid), Ceroplastes spp. (scales),Ceroplastes rubens (red wax scale), Chionaspis spp. (scales),Chrysomphalus spp. (scales), Chrysomphalus aonidum (Florida red scale)Coccus spp. (scales), Coccus pseudomagnoliarum (citricola scale),Dysaphis plantaginea (rosy apple aphid), Empoasca spp. (leafhoppers),Eriosoma lanigerum (woolly apple aphid), Icerya purchasi (cottonycushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphaxstriatellus (smaller brown planthopper), Lepidosaphes spp., Macrosiphumspp., Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium(English grain aphid), Macrosiphum rosae (rose aphid), Macrostelesquadrilineatus (aster leafhopper), Mahanarva frimbiolata, Metopolophiumdirhodum (rose grain aphid), Mictis longicornis, Myzus spp., Myzuspersicae (green peach aphid), Nephotettix spp. (leafhoppers),Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (brownplanthopper), Paratrioza cockerelli (tomato psyllid), Parlatoriapergandii (chaff scale), Parlatoria ziziphi (ebony scale), Peregrinusmaidis (corn delphacid), Philaenus spp. (spittlebugs), Phylloxeravitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale),Planococcus spp. (mealybugs), Planococcus citri (citrus mealybug),Planococcus ficus (grape mealybug), Pseudococcus spp. (mealybugs),Pseudococcus brevipes (pine apple mealybug), Quadraspidiotus pemiciosus(San Jose scale), Rhopalosiphum spp. (aphids), Rhopalosiphum maidis(corn leaf aphid), Rhapalosiphum padi (oat bird-cherry aphid), Saissetiaspp. (scales), Saissetia oleae (black scale), Schizaphis graminum(greenbug), Sitobion avenae (English grain aphid), Sogatella furcifera(white-backed planthopper), Therioaphis spp. (aphids), Toumeyella spp.(scales), Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies),Trialeurodes vaporariorum (greenhouse whitefly), Trialeurodesabutiloneus (bandedwing whitefly), Unaspis spp. (scales), Unaspisyanonensis (arrowhead scale), and Zulia entreriana. In at least someembodiments, the method of the present disclosure may be used to controlMyzus persicae.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hymenoptera (ants, wasps, and sawflies)including, but not limited to, Acromyrrmex spp., Athalia rosae, Attaspp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp.(sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant),Monomorium spp., Monomorium minumum (little black ant), Monomoriumpharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp.(harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fireants), Tapoinoma sessile (odorous house ant), Tetranomorium spp.(pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp.(carpenter bees).

In certain embodiments, the method of the present disclosure may be usedto control members of the Order Isoptera (termites) including, but notlimited to, Coptotermes spp., Coptotermes curvignathus, Coptotermesfrenchii, Coptotermes formosanus (Formosan subterranean termite),Comitermes spp. (nasute termites), Cryptotermes spp. (drywood termites),Heterotermes spp. (desert subterranean termites), Heterotermes aureus,Kalotermes spp. (drywood termites), Incistitermes spp. (drywoodtermites), Macrotermes spp. (fungus growing termites), Marginitermesspp. (drywood termites), Microcerotermes spp. (harvester termites),Microtermes obesi, Procornitermes spp., Reticulitermes spp.(subterranean termites), Reticulitermes banyulensis, Reticulitermesgrassei, Reticulitermes flavipes (eastern subterranean termite),Reticulitermes hageni, Reticulitermes hesperus (western subterraneantermite), Reticulitermes santonensis, Reticulitermes speratus,Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermesspp., and Zootermopsis spp. (rotten-wood termites).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Lepidoptera (moths and butterflies)including, but not limited to, Achoea janata, Adoxophyes spp.,Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (blackcutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana,Amyelosis transitella (navel orangeworm), Anacamptodes defectaria,Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper),Anticarsia gemmatalis (velvetbean caterpillar), Archips argyrospila(fruittree leafroller), Archips rosana (rose leaf roller), Argyrotaeniaspp. (tortricid moths), Argyrotaenia citrana (orange tortrix),Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder),Bucculatrix thurberiella (cotton leafperforator), Caloptilia spp. (leafminers), Capua reticulana, Carposina ruponensis (peach fruit moth),Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneurarosaceana (obliquebanded leafroller), Chlysodeixis spp., Cnaphalocerusmedinalis (grass leafroller), Colias spp., Conpomorpha cramerella,Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydiafunebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Farias insulata(Egyptian bollworm), Farias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobacco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarpa, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth). In at least some embodiments, the methodof the present disclosure may be used to control Spodoptera exigua.

The method of the present disclosure may be used to also control membersof the Order Mallophaga (chewing lice) including, but not limited to,Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken bodylouse), and Menopon gallinea (common hen louse).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Orthoptera (grasshoppers, locusts,and crickets) including, but not limited to, Anabrus simplex (Mormoncricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplusspp. (grasshoppers), Microcentrum retinerve (angularwinged katydid),Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata(forktailed bush katydid), and Valanga nigricorni.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Phthiraptera (sucking lice) including,but not limited to, Haematopinus spp. (cattle and hog lice), Linognathusovillus (sheep louse), Pediculus humanus capitis (human body louse),Pediculus humanus humanus (human body lice), and Pthirus pubis (crablouse).

In particular embodiments, the method of the present disclosure may beused to control members of the Order Siphonaptera (fleas) including, butnot limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis(cat flea), and Pulex irritans (human flea).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Thysanoptera (thrips) including,but not limited to, Caliothrips fasciatus (bean thrips), Caliothripsphaseoli, Frankliniella fusca (tobacco thrips), Frankliniellaoccidentalis (western flower thrips), Frankliniella shultzei,Frankliniella williamsi (corn thrips), Heliothrips haemorrhaidalis(greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp.,Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow teathrips), Taeniothrips rhopalantennalis, Thrips spp., Thrips tabaci(onion thrips), and Thrips hawaiiensis (Hawaiian flower thrips).

The method of the present disclosure may be used to also control membersof the Order Thysanura (bristletails) including, but not limited to,Lepisma spp. (silverfish) and Thermobia spp. (firebrats).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Acari (mites and ticks) including, butnot limited to, Acarapsis woodi (tracheal mite of honeybees), Acarusspp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mangobud mite), Aculops spp., Aculops lycopersici (tomato russet mite),Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rustmite), Amblyomma americanum (lone star tick), Boophilus spp. (ticks),Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and blackflat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks),Dermacentor variabilis (american dog tick), Dermatophagoidespteronyssinus (house dust mite), Eotetranycus spp., Eotetranychuscarpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodesspp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp.,Oligonychus coffee, Oligonychus ilicus (southern red mite), Panonychusspp., Panonychus citri (citrus red mite), Panonychus ulmi (European redmite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemunlatus (broad mite), Rhipicephalus sanguineus (brown dog tick),Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite),Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae(twospotted spider mite), and Varroa destructor (honey bee mite).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Nematoda (nematodes) including, butnot limited to, Aphelenchoides spp. (foliar nematodes), Belonolaimusspp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilariaimmitis (dog heartworm), Ditylenchus spp. (stem and bulb nematodes),Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode),Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lancenematodes), Meloidogyne spp. (root knot nematodes), Meloidogyneincognita (root knot nematode), Onchocerca volvulus (hook-tail worm),Pratylenchus spp. (lesion nematodes), Radopholus spp. (burrowingnematodes), and Rotylenchus reniformis (kidney-shaped nematode).

In at least some embodiments, the method of the present disclosure maybe used to control at least one insect in one or more of the OrdersLepidoptera, Coleoptera, Hemiptera, Thysanoptera, Isoptera, Orthoptera,Diptera, Hymenoptera, and Siphonaptera, and at least one mite in theOrder Acari.

In some embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof a ryanodine receptor modulator compound in combination with apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and wherein theinsect is selected from a sap feeding brown stink bug, Euschistus servus(Say), a lepidopteran diamond back moth, Plutella xylostella (Linnaeus),and a combination thereof.

In one embodiment, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof cyantraniliprole in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and wherein theinsect is selected from a sap feeding brown stink bug, Euschistus servus(Say), a lepidopteran diamond back moth, Plutella xylostella (Linnaeus),and a combination thereof.

In another embodiment, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof chlorantraniliprole in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and wherein theinsect is selected from a sap feeding brown stink bug, Euschistus servus(Say), a lepidopteran diamond back moth, Plutella xylostella (Linnaeus),and a combination thereof.

In a particular embodiment of the present disclosure, the pesticidalcomposition may be used in conjunction (such as, in a compositionalmixture, or a simultaneous or sequential application) with one or morecompounds having acaricidal, algicidal, avicidal, bactericidal,fungicidal, herbicidal, insecticidal, molluscicidal, nematicidal,rodenticidal, and/or virucidal properties.

In certain embodiments of the present disclosure, the pesticidalcomposition may be used in conjunction (such as, in a compositionalmixture, or a simultaneous or sequential application) with one or morecompounds that are antifeedants, bird repellents, chemosterilants,herbicide safeners, insect attractants, insect repellents, mammalrepellents, mating disrupters, plant activators, plant growthregulators, and/or synergists.

The pesticidal compositions of the present disclosure show a synergisticeffect, providing superior pest control at lower pesticidally effectiveamounts of the combined active compounds than when a ryanodine receptormodulator compound or a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof is used alone.

The pesticidal compositions of the present disclosure may have highsynergistic pest control and allow for a lower effective dosage rate, anincreased environmental safety, and a reduced incidence of pestresistance.

The following examples serve to explain embodiments of the presentinvention in more detail. These examples should not be construed asbeing exhaustive or exclusive as to the scope of this disclosure.

EXAMPLES Example 1 Preparation of3-((3,3,3-trifluoropropyl)thio)propanoyl chloride

A dry five-liter round bottom flask equipped with magnetic stirrer,nitrogen inlet, reflux condenser, and thermometer, was charged with3-((3,3,3-trifluoropropyl)thio)propanoic acid (prepared as described inthe PCT Publication No. WO 2013/062981 to Niyaz et al.) (188 g, 883mmol) in dichloromethane (CH₂Cl₂) (3 L). Thionyl chloride (525 g, 321Ml, 4.42 mol) was added dropwise over 50 minutes. The reaction mixturewas heated to reflux (about 36° C.) for two hours, then cooled to roomtemperature (about 22° C.). The resulting mixture was concentrated undervacuum on a rotary evaporator, followed by distillation (40 Ton, productcollected at a temperature of from about 123° C. to about 127° C.) toprovide the title compound as a clear colorless liquid (177.3 g, 86%):¹H NMR (400 MHz, CDCl₃) δ 3.20 (t, J=7.1 Hz, 2H), 2.86 (t, J=7.1 Hz,2H), 2.78-2.67 (m, 2H), 2.48-2.31 (m, 2H); ¹⁹F NMR (376 MHz, CDCl₃) δ−66.42, −66.43, −66.44, −66.44.

Example 2 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I)

To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(prepared as described in the U.S. Publication No. 2012/0110702 to Yapet al.) (10.0 g, 44.9 mmol) in CH₂Cl₂ (100 mL), at a temperature ofabout 0° C. and under N₂, was added pyridine (5.45 mL, 67.4 mmol),4-dimethylaminopyridine (DMAP) (2.74 g, 22.45 mmol), and3-((3,3,3-trifluoropropyl)thio)propanoyl chloride (9.91 g, 44.9 mmol),sequentially. The reaction was warmed to room temperature and stirredfor one hour. The reaction mixture was poured into water (100 mL), andthe resulting mixture was stirred for five minutes. The mixture wastransferred to a separatory funnel, and the layers were separated. Theaqueous phase was extracted with CH₂Cl₂ (3×50 mL), and the combinedorganic extracts were dried over sodium sulfate (Na₂SO₄), filtered, andconcentrated in vacuo. The crude product was purified via normal phaseflash chromatography (0% to 100% EtOAc/CH₂Cl₂) to provide the desiredproduct as a pale yellow solid (17.21 g, 89%): IR (thin film) 1659 cm⁻¹;¹H NMR (400 MHz, CDCl₃) δ 8.95 (d, J=2.6 Hz, 1H), 8.63 (dd, J=4.7, 1.3Hz, 1H), 8.05 (ddd, J=8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H), 7.47 (dd,J=8.3, 4.8 Hz, 1H), 3.72 (q, J=7.1 Hz, 2H), 2.84 (t, J=7.2 Hz, 2H), 2.66(m, 2H), 237 (t, J=7.2 Hz, 2H), 2.44 (m, 2H), 1.17 (t, J=7.2 Hz, 3H);ESIMS m/z 409 ([M+2H]⁺).

Example 3 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II)

To a solution ofN-(3-chloro-1-(20yridine-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) (500 mg, 1.229 mmol) in hexafluoroisopropanol (5 mL) stirring atroom temperature was added 30% hydrogen peroxide (523 mg, 4.92 mmol).The solution was stirred at room temperature for 15 minutes. It wasquenched with saturated sodium sulfite solution and extracted withCH₂Cl₂. Silica gel chromatography (0%-10% MeOH/CH₂Cl₂) gave the titlecompound as white semi-solid (495 mg, 95%): IR (thin film) 1660 cm⁻¹; ¹HNMR (400 MHz, CDCl₃) δ 8.96 (d, J=2.4 Hz, 1H), 8.64 (dd, J=4.7, 1.4 Hz,1H), 8.07-8.00 (m, 2H), 7.46 (ddd, J=8.3, 4.8, 0.7 Hz, 1H), 3.85-3.61(m, 2H), 3.23-3.08 (m, 1H), 3.03-2.76 (m, 3H), 2.74-2.52 (m, 4H), 1.18(t, J=7.2 Hz, 3H); ESIMS m/z 423 ([M+H]⁺).

Example 4

Determination of the Existence of Synergic Effect

The method described in Colby S. R., “Calculating Synergistic andAntagonistic Responses of Herbicide Combinations,” Weeds, 1967, 15,20-22 was used to determine an existence of synergic effect between theryanodine receptor modulator compound and the pesticide (I), (II), orany agriculturally acceptable salt thereof in the formulated pesticidalcomposition. In this method, the percent insect control of theformulated pesticidal composition as observed in the study was comparedto the “expected” percent control (E) as calculated by equation (1)(hereinafter “Colby's equation”) below:

$\begin{matrix}{E = {X + Y - \left( \frac{XY}{100} \right)}} & (1)\end{matrix}$

where

-   -   X is the percentage of control with the first pesticide at a        given rate (p),    -   Y is the percentage of control with the second pesticide at a        given rate (q), and    -   E is the expected control by the first and second pesticide at a        rate of p+q.

If the observed percent control of the formulated pesticidal is greaterthan E, there is a synergistic effect between the ryanodine receptormodulator compound and the pesticide (I), (II), or any agriculturallyacceptable salt thereof in the formulated pesticidal composition. If theobserved percent control of the formulated pesticidal is equaled to orless than E, there is no synergistic effect between the ryanodinereceptor modulator compound and the pesticide (I), (II), or anyagriculturally acceptable salt thereof in the formulated pesticidalcomposition.

Example 5 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)3,3,3-trifluoropropyl)sulfinyl)propanamide (II)and Cyantraniliprole Against Brown Stink Bug, Euschistus heros

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(hereinafter “compound II”) with about 0.000156 weight % ofcyantraniliprole.

Bioassays were performed wherein different active compounds were appliedto the diet of five second-instar nymphs of brown stink bug, Euschistusheros. The percent control determined six days after the diet treatmentwere as shown in TABLE 2. The percent control of the pesticidalcomposition against brown stink bug, Euschistus heros, was determined asthe “Observed” action, and compared to those obtained by using about0.04 weight % of compound II, and using about 0.000156 weight % ofcyantraniliprole alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

TABLE 2 % Control Treatment for Dose Rate Six Days After Brown Stink Bug(weight %) Treatment Compound II 0.04  0% Cyantraniliprole 0.000156  7%Compound II (+) Cyantraniliprole 0.04 + 0.000156 25% Observed ActionCompound II (+) Cyantraniliprole 0.04 + 0.000156  7% Colby's ExpectedAction Compound II (+) Cyantraniliprole 0.04 + 0.000156 18% Differences:Observed vs. Expected

As shown in table 2, the observed percent control of the pesticidalcomposition against brown stink bug (25%) was almost four times higherthan the expected percentage control according to Colby's equation (7%).It was surprising and unexpected that not only there was synergisticeffect between compound II and cyantraniliprole in the pesticidalcomposition against brown stink bug, but also the large magnitude ofsuch synergistic effect. The pesticidal composition showed 257%improvement over the Colby's expected action against brown stink bug.

Example 6 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and Chlorantraniliprole Against Diamond back Moth, Plutellaxylostella Example 6A

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.0003125 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds. Cabbage plantswith about two to three new-growth—true leaf stage were treated withdifferent pesticides using a track sprayer application at 400 L/Ha sprayvolume. Three second instar diamondback moths, Plutella xylostella, wereinfested onto each leaf disc. The percent control determined after threedays of the treatment were as shown in table 3.

TABLE 3 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025 16.67% Chlorantraniliprole0.0003125 66.67% Compound II (+) Chlorantraniliprole 0.0025 + 0.0003125 87.5% Observed Action Compound II (+) Chlorantraniliprole 0.0025 +0.0003125  72.2% Colby's Expected Action Compound II (+)Chlorantraniliprole 0.0025 + 0.0003125  15.3% Differences: Observed vs.Expected

As shown in table 3, the observed percent control of the pesticidalcomposition against diamondback moth (87.5%) was higher than theexpected percentage control according to Colby's equation (72.2%). Thiswas 21% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.0025 weight % of compound II andabout 0.0003125 weight % of chlorantraniliprole showed synergisticeffect against diamondback moth.

Example 6B

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.0000347 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for Example6A. The percent control determined three days after treatment were asshown in table 4.

As shown in table 4, the observed percent control of the pesticidalcomposition against diamondback moth (50%) was higher than the expectedpercentage control according to Colby's equation (37.5%). This was 33%improvement over the Colby's expected action. Therefore, the pesticidalcomposition comprising 0.0025 weight % of compound II and about0.0000347 weight % of chlorantraniliprole showed synergistic effectagainst diamondback moth.

TABLE 4 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025 16.67% Chlorantraniliprole0.0000347   25% Compound II (+) Chlorantraniliprole 0.0025 + 0.0000347  50% Observed Action Compound II (+) Chlorantraniliprole 0.0025 +0.0000347  37.5% Colby's Expected Action Compound II (+)Chlorantraniliprole 0.0025 + 0.0000347  12.5% Differences: Observed vs.Expected

Example 6C

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.000156 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 5.

TABLE 5 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025   0% Chlorantraniliprole0.000156 12.5% Compound II (+) Chlorantraniliprole 0.0025 + 0.00015679.17%  Observed Action Compound II (+) Chlorantraniliprole 0.0025 +0.000156 12.5% Colby's Expected Action Compound II (+)Chlorantraniliprole 0.0025 + 0.000156 66.7% Differences: Observed vs.Expected

As shown in table 5, the observed percent control of the pesticidalcomposition against diamondback moth (79.17%) was significantly higherthan the expected percentage control according to Colby's equation(12.5%). This was 533% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.0025 weight % ofcompound II and about 0.000156 weight % of chlorantraniliprole showedsynergistic effect against diamondback moth.

Example 6D

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.0000781 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 6.

TABLE 6 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025   0% Chlorantraniliprole0.0000781 4.17% Compound II (+) Chlorantraniliprole 0.0025 + 0.000078141.67%  Observed Action Compound II (+) Chlorantraniliprole 0.0025 +0.0000781  4.2% Colby's Expected Action Compound II (+)Chlorantraniliprole 0.0025 + 0.0000781 37.5% Differences: Observed vs.Expected

As shown in table 6, the observed percent control of the pesticidalcomposition against diamondback moth (41.67%) was significantly higherthan the expected percentage control according to Colby's equation(4.2%). This was 892% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.0025 weight % ofcompound II and about 0.0000781 weight % of chlorantraniliprole showedsynergistic effect against diamondback moth.

Example 6E

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound II with about 0.000104 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 7.

TABLE 7 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.000625 16.67% Chlorantraniliprole 0.000104 62.5% Compound II (+) Chlorantraniliprole0.000625 + 0.000104 95.83%  Observed Action Compound II (+)Chlorantraniliprole 0.000625 + 0.000104 68.8% Colby's Expected ActionCompound II (+) Chlorantraniliprole 0.000625 + 0.000104 27.1%Differences: Observed vs. Expected

As shown in table 7, the observed percent control of the pesticidalcomposition against diamondback moth (95.83%) was higher than theexpected percentage control according to Colby's equation (68.8%). Thiswas 39% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.000625 weight % of compound II andabout 0.000104 weight % of chlorantraniliprole showed synergistic effectagainst diamondback moth.

Example 6F

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound II with about 0.000156 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 8.

As shown in table 8, the observed percent control of the pesticidalcomposition against diamondback moth (66.67%) was substantially higherthan the expected percentage control according to Colby's equation(16.1%). This was 314% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.000625 weight % ofcompound II and about 0.000156 weight % of chlorantraniliprole showedsynergistic effect against diamondback moth.

TABLE 8 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.000625 4.17% Chlorantraniliprole0.000156 12.5% Compound II (+) Chlorantraniliprole 0.000625 + 0.00015666.67%  Observed Action Compound II (+) Chlorantraniliprole 0.000625 +0.000156 16.1% Colby' s Expected Action Compound II (+)Chlorantraniliprole 0.000625 + 0.000156 50.5% Differences: Observed vs.Expected

Example 6G

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound II with about 0.0000781 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 9.

As shown in table 9, the observed percent control of the pesticidalcomposition against diamondback moth (50%) was substantially higher thanthe expected percentage control according to Colby's equation (8.2%).This was 510% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.000625 weight % of compound IIand about 0.0000781 weight % of chlorantraniliprole showed synergisticeffect against diamondback moth.

TABLE 9 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.000625 4.17% Chlorantraniliprole0.0000781 4.17% Compound II (+) Chlorantraniliprole 0.000625 + 0.0000781  50% Observed Action Compound II (+) Chlorantraniliprole 0.000625 +0.0000781  8.2% Colby' s Expected Action Compound II (+)Chlorantraniliprole 0.000625 + 0.0000781 41.8% Differences: Observed vs.Expected

Example 7 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and Cyantraniliprole Against Diamondback Moth, Plutella xylostellaExample 7A

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.0003125 weight % ofcyantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 10.

As shown in table 10, the observed percent control of the pesticidalcomposition against diamondback moth (79.17%) was substantially higherthan the expected percentage control according to Colby's equation(29.2%). This was 171% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.0025 weight % ofcompound II and about 0.0003125 weight % of cyantraniliprole showedsynergistic effect against diamondback moth.

TABLE 10 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025    0% Cyantraniliprole0.0003125 29.17% Compound II (+) Cyantraniliprole 0.0025 + 0.000312579.17% Observed Action Compound II (+) Cyantraniliprole 0.0025 +0.0003125  29.2% Colby's Expected Action Compound II (+)Cyantraniliprole 0.0025 + 0.0003125  50.0% Differences: Observed vs.Expected

Example 7B

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.000156 weight % ofcyantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 11.

TABLE 11 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025  0% Cyantraniliprole0.000156 25% Compound II (+) Cyantraniliprole 0.0025 + 0.000156 70.83%  Observed Action Compound II (+) Cyantraniliprole 0.0025 + 0.000156 25%Colby's Expected Action Compound II (+) Cyantraniliprole 0.0025 +0.000156 45.8%   Differences: Observed vs. Expected

As shown in table 11, the observed percent control of the pesticidalcomposition against diamondback moth (70.83%) was substantially higherthan the expected percentage control according to Colby's equation(25%). This was 183% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.0025 weight % ofcompound II and about 0.000156 weight % of cyantraniliprole showedsynergistic effect against diamondback moth.

Example 7C

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound II with about 0.0000781 weight % ofcyantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 12.

TABLE 12 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.0025  0% Cyantraniliprole0.0000781 25% Compound II (+) Cyantraniliprole 0.0025 + 0.000078166.67%   Observed Action Compound II (+) Cyantraniliprole 0.0025 +0.0000781 25% Colby's Expected Action Compound II (+) Cyantraniliprole0.0025 + 0.0000781 41.7%   Differences: Observed vs. Expected

As shown in table 12, the observed percent control of the pesticidalcomposition against diamondback moth (66.67%) was higher than theexpected percentage control according to Colby's equation (25%). Thiswas 167% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.0025 weight % of compound II andabout 0.0000781 weight % of cyantraniliprole showed synergistic effectagainst diamondback moth.

Example 7D

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound II with about 0.0003125 weight % ofcyantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth using the same procedure as that described for example6A. The percent control determined three days after treatment were asshown in table 13.

TABLE 13 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound II 0.000625 4.17% Cyantraniliprole0.0003125 29.17%  Compound II (+) Cyantraniliprole 0.000625 + 0.0003125 100% Observed Action Compound II (+) Cyantraniliprole 0.000625 +0.0003125 32.1% Colby's Expected Action Compound II (+) Cyantraniliprole0.000625 + 0.0003125 67.9% Differences: Observed vs. Expected

As shown in table 13, the observed percent control of the pesticidalcomposition against diamondback moth (100%) was higher than the expectedpercentage control according to Colby's equation (32.1%). This was 212%improvement over the Colby's expected action. Therefore, the pesticidalcomposition comprising 0.000625 weight % of compound II and about0.0003125 weight % of cyantraniliprole showed synergistic effect againstdiamondback moth.

Example 8 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and Chlorantraniliprole Against Diamondback Moth, Plutellaxylostella Example 8A

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(hereinafter “compound I”) with about 0.0000781 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds. Cabbage plantswith about two to three new-growth—true leaf stage were treated withdifferent pesticides using a track sprayer at a rate of 400 L/Ha. Threesecond instar diamondback moths, Plutella xylostella, were infested ontoeach leaf disc. The percent control determined three days aftertreatment were as shown in table 14.

TABLE 14 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound I 0.0025  4.35% Chlorantraniliprole0.0000781 30.43% Compound I (+) Chlorantraniliprole 0.0025 + 0.000078182.61% Observed Action Compound I (+) Chlorantraniliprole 0.0025 +0.0000781 33.46% Colby's Expected Action Compound I (+)Chlorantraniliprole 0.0025 + 0.0000781 49.51% Differences: Observed vs.Expected

As shown in table 14, the observed percent control of the pesticidalcomposition against diamondback moth (82.61%) was higher than theexpected percentage control according to Colby's equation (30.43%). Thiswas about 147% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.0025 weight % of compound I andabout 0.0000781 weight % of chlorantraniliprole showed significantsynergistic effect against diamondback moth, Plutella xylostella.

Example 8B

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound I with about 0.000156 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth, Plutella xylostella, according to the proceduredescribed in example 8A. The percent control determined three days aftertreatment were as shown in table 15.

TABLE 15 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound I 0.000625    0% Chlorantraniliprole0.000156 73.91% Compound I (+) Chlorantraniliprole 0.000625 + 0.00015691.30% Observed Action Compound I (+) Chlorantraniliprole 0.000625 +0.000156 73.91% Colby' s Expected Action Compound I (+)Chlorantraniliprole 0.000625 + 0.000156 17.39% Differences: Observed vs.Expected

As shown in table 15, the observed percent control of the pesticidalcomposition against diamondback moth (91.30%) was higher than theexpected percentage control according to Colby's equation (73.91%). Thiswas about 23.5% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.000625 weight % of compound Iand about 0.000156 weight % of chlorantraniliprole showed synergisticeffect against diamondback moth, Plutella xylostella.

Example 8C

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound I with about 0.0000781 weight % ofchlorantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth, Plutella xylostella, according to the proceduredescribed in example 8A. The percent control determined three days aftertreatment were as shown in table 16.

TABLE 16 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound I 0.000625    0% Chlorantraniliprole0.0000781 30.43% Compound I (+) Chlorantraniliprole 0.000625 + 0.000078169.56% Observed Action Compound I (+) Chlorantraniliprole 0.000625 +0.0000781 30.43% Colby's Expected Action Compound I (+)Chlorantraniliprole 0.000625 + 0.0000781 39.13% Differences: Observedvs. Expected

As shown in table 16, the observed percent control of the pesticidalcomposition against diamondback moth (69.56%) was higher than theexpected percentage control according to Colby's equation (30.43%). Thiswas about 128.6% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.000625 weight % ofcompound I and about 0.0000781 weight % of chlorantraniliprole showedsignificant synergistic effect against diamondback moth, Plutellaxylostella.

Example 9 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and Cyantraniliprole Against Diamondback Moth, Plutella xylostellaExample 9A

A pesticidal composition was prepared by thoroughly mixing about 0.0025weight % of compound I with about 0.000156 weight % of cyantraniliprole.

Bioassays were performed for different active compounds. Cabbage plantswith about two to three new-growth—true leaf stage were treated withdifferent pesticides using a track sprayer at a rate of 400 L/Ha. Threesecond instar diamondback moths, Plutella xylostella, were infested ontoeach leaf disc. The percent control determined three days aftertreatment were as shown in table 17.

TABLE 17 % Control Treatment for Dose Rate Three Days Diamondback Moth(weight %) After Treatment Compound I 0.0025  4.35% Cyantraniliprole0.000156 73.91% Compound I (+) Cyantraniliprole 0.0025 +  91.3% ObservedAction 0.000156 Compound I (+) Cyantraniliprole 0.0025 + 75.04% Colby'sExpected Action 0.000156 Compound I (+) Cyantraniliprole 0.0025 + 16.26%Differences: Observed vs. Expected 0.000156

As shown in table 17, the observed percent control of the pesticidalcomposition against diamondback moth (91.3%) was higher than theexpected percentage control according to Colby's equation (75.04%). Thiswas about 21.67% improvement over the Colby's expected action.Therefore, the pesticidal composition comprising 0.0025 weight % ofcompound II and about 0.000156 weight % of cyantraniliprole showedsynergistic effect against diamondback moth.

Example 9B

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound I with about 0.0003125 weight % ofcyantraniliprole.

Bioassays were performed for different active compounds againstdiamondback moth, Plutella xylostella, according to the proceduredescribed in example 9A. The percent control determined three days aftertreatment were as shown in table 18.

As shown in table 18, the observed percent control of the pesticidalcomposition against diamondback moth (100%) was higher than the expectedpercentage control according to Colby's equation (91.30%). This wasabout 9.53% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.000625 weight % of compound II andabout 0.0003125 weight % of cyantraniliprole showed synergistic effectagainst diamondback moth.

TABLE 18 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound I 0.000625    0% Cyantraniliprole0.0003125 91.30% Compound I (+) Cyantraniliprole 0.000625 + 0.0003125  100% Observed Action Compound I (+) Cyantraniliprole 0.000625 +0.0003125 91.30% Colby's Expected Action Compound I (+) Cyantraniliprole0.000625 + 0.0003125  8.70% Differences: Observed vs. Expected

Example 10 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and Flubendiamide Against Diamondback Moth, Plutella xylostella

A pesticidal composition was prepared by thoroughly mixing about0.000625 weight % of compound I with about 0.0003125 weight % offlubendiamide.

Bioassays were performed for different active compounds againstdiamondback moth, Plutella xylostella, according to the proceduredescribed in example 9A. The percent control determined three days aftertreatment were as shown in table 19.

As shown in table 19, the observed percent control of the pesticidalcomposition against diamondback moth (17.39%) was higher than theexpected percentage control according to Colby's equation (8.70%). Thiswas almost 100% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.0025 weight % of compound I andabout 0.0003125 weight % of flubendiamide showed synergistic effectagainst diamondback moth, Plutella xylostella.

TABLE 19 % Control Three Days Treatment for Dose Rate After DiamondbackMoth (weight %) Treatment Compound I 0.0025   0% Flubendiamide 0.00031258.70% Compound I (+) Flubendiamide 0.0025 + 0.0003125 17.39%  ObservedAction Compound I (+) Flubendiamide 0.0025 + 0.0003125 8.70% Colby'sExpected Action Compound I (+) Flubendiamide 0.0025 + 0.0003125 8.69%Differences: Observed vs. Expected

Prophetic example PE-11 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and Cyantraniliprole, Chlorantraniliprole, or Flubendiamide

A pesticidal composition may be prepared by thoroughly mixing compound I(weight %) or compound II (weight %) with cyantraniliprole,chlorantraniliprole, or flubendiamide (weight %).

The bioassays may be performed for different active compounds againstbrown stink bug, Euschistus heros, using the same procedure as thatdescribed in example 5. The percent control may be determined some timeafter treatment.

The bioassays may be performed for different active compounds againstdiamondback moth, Plutella xylostella, using the same procedure as thatdescribed for example 6A. The percent control may be determined sometime after treatment.

The observed percent control of the pesticidal composition against brownstink bug is expected to be higher than the expected percentage controlaccording to Colby's equation. Therefore, the pesticidal compositioncomprising compound I (weight %) or compound II (weight %) andcyantraniliprole, chlorantraniliprole, or flubendiamide (weight %) isexpected to show synergistic effect against brown stink bug.

The observed percent control of the pesticidal composition againstdiamondback moth is expected to be higher than the expected percentagecontrol according to Colby's equation. Therefore, the pesticidalcomposition comprising compound I (weight %) or compound II (weight %)and cyantraniliprole, chlorantraniliprole, or flubendiamide (weight %)is expected to show synergistic effect against diamondback moth.

While the present disclosure may be susceptible to various modificationsand alternative forms, specific embodiments have been described by wayof example in detail herein. However, it should be understood that thepresent disclosure is not intended to be limited to the particular formsdisclosed. Rather, the present disclosure is to cover all modifications,equivalents, and alternatives falling within the scope of the presentdisclosure as defined by the following appended claims and their legalequivalents.

We claim:
 1. A pesticidal composition comprising a synergisticallyeffective amount of: a ryanodine receptor modulator compound; and apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.


2. The composition of claim 1, further comprising aphytologically-acceptable inert carrier.
 3. The composition of claim 1,further comprising an additive selected from a surfactant, a stabilizer,an emetic agent, a disintegrating agent, an antifoaming agent, a wettingagent, a dispersing agent, a binding agent, dye, filler, andcombinations thereof.
 4. The composition of claim 1, further comprisingone or more compounds having acaricidal, algicidal, avicidal,bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal,nematicidal, rodenticidal, virucidal or combinations thereof properties.5. The composition of claim 1, further comprising one or more compoundsthat are antifeedants, bird repellents, chemosterilants, herbicidesafeners, insect attractants, insect repellents, mammal repellents,mating disrupters, plant activators, plant growth regulators,synergists, or combinations thereof.
 6. The composition of claim 1,wherein a weight ratio of the pesticide selected from (I), (II) or anyagriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 256:1.
 7. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 72:1.
 8. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 32:1.
 9. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 16:1.
 10. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 8:1.
 11. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 6:1.
 12. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 4:1.
 13. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the ryanodine receptormodulator compound is no more than about 2:1.
 14. The composition ofclaim 1, wherein the weight ratio of the pesticide (I), (II), or anyagriculturally acceptable salt thereof and the ryanodine receptormodulator is X:Y; wherein, X is the parts by weight of the pesticide(I), (II), or any agriculturally acceptable salt thereof, and thenumerical range is 0<X≦20; Y is the parts by weight of the ryanodinereceptor modulator, and the numerical range is 0<Y≦20.
 15. A method ofcontrolling pests comprising applying the pesticidal composition ofclaim 1, near a population of pests, in an amount sufficient to controlthe pests.
 16. The method of claim 15, wherein the pests are brown stinkbug (Euschistus heros), diamond back moth (Plutella xylostella), or acombination thereof.
 17. The method of claim 15, wherein the pestsinclude a member selected from Order Lepidoptera , Coleoptera, Diptera,Isoptera species, and combinations thereof.
 18. The method of claim 15,wherein the ryanodine receptor modulator compound compriseschlorantraniliprole, cyantraniliprole, or a mixture thereof.
 19. Themethod of claim 15, wherein the ryanodine receptor modulator compoundcomprises chlorantraniliprole, cyantraniliprole, cyclaniliprole,flubendiamide, or mixtures thereof.